Catalyst, Catalyst Support And Process For Hydrogenation, Hydroisomerization, Hydrocracking And/Or Hydrodesulfurization

ABSTRACT

Described are catalysts for the hydrogenation, hydroisomerisation, hydrocracking and/or hydrodesulfurisation, of hydrocarbon feedstocks, the catalysts comprising a substantially binder free bead type support material comprising 5 to 60 wt. % of at least one crystalline molecular sieve material and 40 to 95 wt. % of non-crystalline, non-zeolitic silica-alumina and a catalytically active component comprising precious metals. Also described are methods for making catalyst supports by the dropwise addition of an aqueous sol of inorganic salts of aluminum and silicon, having dispersed therein the crystalline molecular sieve material, through an oil-phase to a water phase, thus providing homogeneous beads that are obtained without a separate shape-forming step.

The present invention is directed to a catalyst, a support for acatalyst and a process for hydrogenation, hydroisomerization,hydrocracking and/or hydrodesulfurization of a sulfur contaminants andoptionally nitrogen contaminants containing feedstock.

When hydrogenation catalysts are used in the hydrogenation of petroleumdistillates and derivatives thereof, often a problem presents itself inthat the feed comprises as contaminants sulfur components and optionallynitrogen components, which adversely affect the life-time of thecatalyst. In such processes conventional hydrogenation catalysts areusually applied, for instance supported nickel or platinum catalysts. Toreduce this problem of deactivation much attention has been paid to theremoval of at least part of the sulfur compounds from the gaseous orliquid feed prior to the hydrogenation. This method is also known ashydrodesulfurization (HDS). Feeds containing sulfur contaminants mayalso contain nitrogen contaminants, which also can act as catalystpoison.

In general sulfur impurities are present in feeds as mercaptans orthiophenic compounds, more in particular thiophene, benzothiophene,dibenzothiophene, as well as substitution products thereof, whichimpurities can be converted to H₂S and hydrocarbons using a sulfidizedCo—Mo catalyst.

The H₂S produced in the HDS process is generally in the gaseous phaseand is usually adsorbed from the gaseous phase by the use of a suitablesolvent or solvent mixture, and processed into elemental sulfur.

The liquid product stream obtained from the HDS process still containssome sulfur. Typical sulfur levels of these product streams fromHDS-units range from 0.1 to 500 ppm.

When nickel is used as a catalyst in the subsequent hydrogenation step,the major part of the sulfur is taken up by the nickel. As a result, thenickel catalyst will be deactivated in the course of time.

Similar problems to those described above may occur inhydroisomerization processes of sulfur containing feedstocks, catalyzedby a metal catalyst on a support. In these processes, the carbon chainof a paraffin is converted into a different carbon chain having the samecarbon to hydrogen ratio.

While the deterioration of nickel catalysts caused by sulfur poisoningis in practice an irreversible process, noble metal catalysts retainpart of their activity in the presence of sulfur contaminants. Thesensitivity of noble metals to sulfur is related to the properties ofthe support and the metal(s) used.

In U.S. Pat. No. 3,943,053 it has been proposed to use a catalyst of analloy of platinum and palladium in a weight ratio of approximately 1:3on a chlorinated alumina support for the hydrogenation of aromatics andolefins present in hydrocarbon fractions containing sulfur and nitrogencompounds. This catalyst was reported to decrease the amount ofaromatics in an effluent by 66% compared to catalysts of the singlemetals.

The French patent application 2 569 995 describes the use of a catalystbased on vermiculite having a molar ratio of silica:alumina of at least12:1 and a high specific surface area. The catalyst further comprises atleast one metal or compound thereof chosen from Group VIII of thePeriodic Table. The most preferred catalyst described in said Frenchpatent application comprises at least one oxide of a metal chosen fromGroup VIII of the Periodic Table in combination with at least one oxideof a metal chosen from Group VI of the Periodic Table on saidvermiculite support.

In EP-A 540,123 extrudates of alumina, silica-alumina and zeolite havebeen described, having Pt and Pd deposited thereon. The activity of thismaterial is limited.

The European patent application 0 669 162 discloses a catalyst for aprocess for reducing the aromatic content of a hydrocarbon stream. Saidcatalyst comprises a specific silica-alumina carrier on which one ormore metals of Group VIII of the Periodic Table are deposited.

A disadvantage of this catalyst is that the specific silica-aluminacarrier is obtained from a solution of an aluminum alcoholate and/orcarboxylate and a silicon alcoholate and/or carboxylate. The use ofthese organic starting materials for preparing the carrier isenvironmentally unattractive. Furthermore, the preparation of thecarrier involves the extrusion of a viscous paste, which is anadditional process step.

In EP-A 582,347 a similar catalyst, having the same disadvantages hasbeen proposed as hydro-isomerisation catalyst. A particular disadvantageof this catalyst is the small pore size, 1-3 nm, making it rather lesssuitable for treatment of heavy feedstocks. Further no information isgiven about the behavior in an environment where sulfur contaminants arealso present.

In WO-A 9835754 a considerable improvement of the prior art catalystshas been proposed. This document describes catalysts based onnon-crystalline silica-alumina supports, prepared by sol-gel techniques,said techniques encompassing first preparing a sol of silica-alumina,which is then gelled by passing sol-droplets consecutively through anoil phase and an aqueous alkaline phase.

Other catalysts of platinum and palladium are disclosed in U.S. Pat. No.5,308,814 and international patent application WO-A-94/19429. In thefirst document the disclosed catalyst is supported on a zeolite Ysupport and in the latter on a zeolite beta support.

Although the catalysts of noble metals, such as platinum, palladium,ruthenium, iridium and rhodium, on zeolite supports appear to be moreactive than those on e.g. alumina, they have some disadvantages. It wasfound that hydrogenation, hydroisomerization, hydrocracking and/orhydrodesulfurization using a catalyst based on platinum, palladium or acombination thereof on a zeolite support tends to become more difficultwhen the used feedstock is heavier. Furthermore, some of these zeolitesare expensive materials, thus rendering the use of catalysts on thesezeolite supports economically less attractive.

Even though some of the processes mentioned above provide for animprovement in the hydrogenation of sulfur contaminant containingfeedstocks, there is still room for improvement, more in particular inthe properties of the hydrogenated compounds and in terms of activity.

It is therefore an object of the invention to provide a novel catalystfor hydrogenation, hydroisomerization, hydrocracking and/orhydrodesulfurization of a sulfur and optionally nitrogen contaminantcontaining feedstock, said catalyst having a low sensitivity topoisoning by said contaminants.

It is a further object of the invention to provide a process forhydrogenation, hydroisomerization, hydrocracking and/orhydrodesulfurization of a sulfur contaminant containing feedstock,wherein a catalyst is used which has a high hydrogenation,hydroisomerization, hydrocracking and/or hydrodesulfurization activity.

Still another object of the invention is to provide a process forhydrogenation, hydroisomerization, hydrocracking and/orhydrodesulfurization of a sulfur contaminant containing feedstock,wherein both light and heavy feedstocks may be hydrogenated,hydroisomerized, hydrocracked and/or hydrodesulfurized.

Yet another object of the invention is to provide a process forhydrogenation, hydroisomerization, hydrocracking and/orhydrodesulfurization of a sulfur contaminant containing feedstock, whichprocess combines the above objects in an optimal manner, i.e. wherein acatalyst having a well-balanced, fine-tuned profile of all the abovedesired qualities and characteristics is used.

The present invention is based on the surprising discovery, that thecombination of a molecular sieve material (such as zeolites in thebroadest sense of the term) and a non-crystalline silica-alumina in asubstantially binder free support material, results in both animprovement of the activity of a precious metal catalyst and in animprovement in the performance of the catalyst, namely resulting inimproved properties of the hydrogenated feedstock.

The present invention accordingly is directed to a Catalyst for thehydrogenation, hydro-isomerisation, hydrocracking and/orhydrodesulfurisation, of hydrocarbon feedstocks, said catalystconsisting of a substantially binder free bead type support materialobtained through a sol-gel method, and a catalytically active componentselected from precious metals, the support comprising 5 to 50 wt. % ofat least one molecular sieve material and 50 to 95 wt. % ofsilica-alumina and up to 5 wt. % of binder. More in particular thesupport material is completely binder free.

Preferred embodiments have been defined in the dependent claims.

Compared to conventional materials that contain more than 20 wt. % oreven up to 30 wt. % of binder material, the present invention providesfor a substantial improvement. The absence of binder material results ina substantial increase in the number of catalytically active sites andthus in the loading of the reactor. Additionally it is to be noted thatthe activity per amount of precious metal is improved. Further, by usingthis combination of molecular sieve material and silica-alumina, it ispossible to obtain hydrogenated feedstocks having improved propertiessuch as diesel fuels with better cetane number. Generally, the cetanenumber of diesel can be improved by hydrogenating aromatic rings and/orby opening naphtenic rings. These improvements are even more pronouncedin case use is made of sol-gel techniques, as defined herein, for thepreparation of the support material.

An important advantage of the invention resides therein that the supportof the catalyst consists of beads which have a much higher mechanicalstrength than the conventional extruded supports. At the same time, theactivity of the noble metal of a catalyst which is used in a processaccording to the invention is about equal or higher compared to that ofsimilar catalysts having comparable active noble metal surfaces, asdefined by CO adsorption. In other words, according to the invention ahigher activity per unit reactor volume is achieved when compared to theprocess disclosed in EP-A-0 540 123, while the same amount of catalystis used.

The invention is further directed to a catalyst or catalyst support,consisting of a substantially binder free support material comprising 5to 50 wt. % of at least one molecular sieve material and 50 to 95 wt. %of silica-alumina. This material may either be used as support for acatalytically active material, which support has acidic properties or asa catalyst for acid catalyzed reactions, such as isomerisation,alkylation or (de)hydration reactions in general. In this embodiment thematerial of the invention is characterized by the possibility to tunethe acidity and the absence of binder, without the inherently expectedproblems of this absence.

The invention is also directed to a process comprising in its mostgeneral form reactions in which hydrocarbon feedstocks are hydrogenatedor dehydrogenated. More in particular hydrocarbon feedstocks containingsulfur contaminants are reacted in the presence of hydrogen. Animportant class of these feedstocks is formed by the various sulfurcontaining petroleum distillates and derivatives thereof.

Typical feedstocks to be hydrogenated, hydroisomerized, hydrocrackedand/or hydrodesulfurized in the process of the invention usually have asulfur contaminant content of from 0.1 to 500 ppm, preferably from 0.1to 300 ppm calculated as sulfur, based on the weight of the feedstock.Examples of such feeds are inter alia benzene, “white oils”, gasoline,middle distillates, such as diesel and kerosene, solvents and resins.More in particular the process is to be used for hydrogenating aromaticcompounds in these feedstocks, e.g. dearomatizing hydrocarbon feeds thatmay contain thiophenic sulfur contaminants and/or nitrogen containingcontaminants.

Surprisingly, it has further been found that olefins in an aromaticfeedstock may be selectively hydrogenated in a process according to theinvention. Particularly when a catalyst comprising only palladium isused, this hydrogenation of olefins in an aromatic feedstock is highlyefficient.

In a specific embodiment, the catalyst of the invention is combined witha nickel catalyst in accordance with the procedure described ininternational patent application WO-A-97/03150. In a process inaccordance with this embodiment, a hydrocarbon feed containing sulfurcontaminants is contacted with the catalyst of the invention prior to orsimultaneously with contacting a nickel catalyst. In this manner, thesulfur resistance of a nickel catalyst is improved and a very longlife-time is obtained.

The process according to the invention can be carried out in varioustypes of reactors which are suitable for hydrogenation, such as solidbed reactors, fluid bed reactors, slurry-phase reactors, trickle-phasereactors and the like.

In different embodiments of the process of the invention modificationscan be made in reactor configuration and process design, at least partlydepending on the nature of the feed and the temperature required for thedesired reaction.

The process conditions are the known ones used for the hydrogenation,hydroisomerization, hydrocracking and/or hydrodesulfurization of thefeeds used.

The hydrogen (partial) pressure used for the hydrogenation,hydroisomerization, hydrocracking and/or hydrodesulfurization depends onthe type of feed and is preferably of from 0.5 to 300 bar, morepreferably of from 0.9 to 250 bar.

Generally suitable conditions for the process according to the inventionfurther comprise temperatures between 50 and 450° C. and liquid hourlyspace velocities (LHSV) between 0.1 and 25 h⁻¹. Depending on the type offeedstock and the hydrogen partial pressure, the temperature cansuitably be chosen within the said range. More in particular it is to benoted that hydrocracking requires the highest temperature range, i.e. upto 450° C., whereas for hydrodesulfurization temperatures up to 400° C.suffice. Hydrogenation and hydroisomerization can be performed usingtemperatures of up to 350° C.

Various heavier feeds, especially those containing sulfur compoundshaving a higher boiling point, such as benzothiophene, dibenzothiopheneand substituted dibenzothiophenes, require a rather high temperature forthe hydrogenation, with the result that the temperature to be used forthe process corresponds to the temperature at which the catalyticallyactive materials, more in particular platinum, palladium or combinationthereof are most effective.

As has been mentioned above, an important aspect of the invention,leading to the advantageous process for hydrogenation,hydroisomerization, hydrocracking and/or hydrodesulfurization of asulfur contaminant containing hydrocarbon feedstock, is the choice of avery specific catalyst. Thus, the invention also relates to a catalystfor use in a hydrogenation, hydroisomerization, hydrocracking and/orhydrodesulfurization process as described above.

According to a preferred embodiment of the invention the catalyst has adispersion degree of at least 0.2. The dispersion degree as definedherein is an important aspect of the catalyst of this embodiment. Thedispersion degree is defined as the ratio of the number of CO moleculesadsorbed in the first pulse, determined as set forth hereinbelow, andthe number of metal atoms present in the catalyst sample.

In the support an amount of molecular sieve material, generally acrystalline micro- or mesoporous material, such as zeolite, modifiedzeolite or aluminium phosphate, preferably a zeolite in acidic form, ispresent. The term zeolite or modified zeolite is used to indicate thatnot only the traditional zeolite materials based on Si and Al areencompassed, but also other materials, such as titanium based zeolites.

The amount of molecular sieve material can be between 5 and 50 wt. %,preferably between 15 and 40 wt. %. Suitable zeolites are the acidiczeolites, such as the acidic forms of Zeolite X, Y, β, MCM-41, ZSM-5,modifications thereof and the like. Other possible materials are thealuminium phosphates.

The silica-alumina present in the support of the catalyst according tothe invention is non-crystalline, in contrast to the molecular sievematerial, which is crystalline. Crystallinity is generally determined byX-ray diffraction. A non-crystalline silica-alumina (more in particulara non-zeolitic material) has an X-ray diffraction pattern, which doesnot exhibit any diffraction peaks with a width at half height less than1.0 degree of arc (measured over the double diffraction angle).

The acidity of the silica-alumina/zeolite support can for example bemeasured using pyridine adsorption/desorption, as described in theExperimental part.

However, according to a preferred embodiment the material has acidicproperties, more in particular a Brønsted acidity of at least 5 μmol/g,as defined in the experimental part. More in particular the lower limitis 25, most preferred 50 μmol/g.

In this regard it is to be noted that applying the catalytically activemetal to the support does not have a large influence on the acidity,especially not at noble metal loadings below 2 wt. %.

The support of the catalyst is obtained by sol-gel techniques, which arehighly attractive from an environmental point of view. These techniquesare described in for instance EP-A-0 090 994 and comprise the dropwiseaddition of an aqueous sol of inorganic salts of aluminum and silicon,containing dispersed therein the molecular sieve material, through anoil-phase to an alkaline water phase. This way, homogeneous beads areobtained which have a uniform porosity.

An advantage of preparing the support in this specific manner is thatbeads are obtained without performing a separate shape forming step suchas extrusion. Moreover, beads can be handled very conveniently andsafely during loading and unloading of a reaction vessel and enable avery high degree of packing in a reaction vessel due to their nearlyspherical shape.

Another advantage of preparing the support by this sol-gel preparationmethod is that the obtained support has a very high mechanic strengthand gives rise to hardly any production of fines, if at all. Both theBulk Crush Strength (BCS) and the Side Crush Strength (SCS) of thesupport have very high values.

In the British patent 790,476 a catalyst comprising platinum and/orpalladium on a silica-alumina support, has been disclosed, which supportmay be obtained by a sol-gel technique. This catalyst is, however, acatalyst for a process of reforming hydrocarbon fractions. Also, thepreparation of the silica-alumina support described in this documentcomprises the preparation of a silica support by a sol-gel technique,wherein the alumina is introduced later by an ion-exchange method or asubsequent impregnation step. The described preparation leads to asupport having a smaller surface area than that of the support of thecatalyst which is used in accordance with the present invention.

The silica-alumina support of the catalyst to be used in the presentinvention may have a surface area chosen in the range of from 25 to 1200m²/g, preferably in the range of from 25 to 1000 m²/g. More preferably,the surface area of the support ranges from 200 to 1000 m²/g. It wasfound that a support having a surface area falling within the specifiedranges renders a catalyst the most active.

The average pore size (calculated from the pore volume (<60 nm) and thesurface area (BET), assuming cylindrical pores) of the support of acatalyst used in a process according to the invention is preferablyhigher than 2.0 nm, more preferably higher than 2.5 nm. It has beenfound, that applying the metal component to the support does notsignificantly alter the average pore size.

According to the invention, the Si/Al atomic ratio is of from 1:10 to200:1, preferably of from 1:10 to 100:1. It is most preferred to have aSi/Al atomic ratio of from 1:3 to 50:1. Within this range an optimalincrease in activity is observed.

Preferably, the catalyst comprises at least 0.01, more preferably 0.01to 5, and most preferably 0.1 to 2, weight percent of the noble metal,i.e. rhodium, ruthenium, iridium, platinum, palladium or a combinationthereof, based on the weight of the catalyst.

The catalyst preferably comprises both platinum and palladium. In thispreferred embodiment, the platinum and palladium used in the catalyst ofthe invention are preferably present in a weight ratio of from 10:1 to1:10, more preferably of 5:1 to 1:5. It is remarked, that it isuncertain in which chemical form the metal is active. This may be thepure metal, but it is also possible that the metal sulfide, or a metalalloy, is at least partly responsible for the increase in the sulfurresistance.

The catalyst which is used in accordance with the invention can beprepared by applying the noble metal component on the support having therequired characteristics. Examples of such preparations and theconditions thereof are known to the skilled person. The application ofthe active metal component and/or components or precursors thereof tothe support material can be performed by means of impregnation,adsorption, ion-exchange, chemical vapor deposition (CVD) orprecipitation, if necessary, followed by further treatment to convertthe precursor to the actual catalyst.

The invention also encompasses the use of a non-crystalline, acidicsupport for improving the performance of a catalyst based on platinum,palladium or a combination thereof in hydrogenation, hydroisomerization,hydrocracking and/or hydrodesulfurization reactions of a sulfurcontaminant containing feedstock.

EXPERIMENTAL

In order to obtain the data listed in the examples, the followingmethods were employed.

Acidity of Catalysts

Pyridine adsorption experiments were done in a diffuse reflectance hightemperature chamber equipped with KBr windows(Spectra-Tech). The chamberwas connected with a gas system so that gases can flow through thechamber and the chamber can be evacuated.

Samples were ground into a fine powder and put into an aluminum samplecup. The samples were first heated to 450° C. and held at 450° C. for atleast 1 h while a flow of inert gas was led through the chamber. Aftercooling to ambient temperature, a pyridine inert gas mixture was ledthrough the chamber for about 1 min. Subsequently, the pyridine flow wasstopped, while the flow of inert gas continued and the system was keptin this mode for at least 1 h. Finally, the sample was heated to 180° C.in the flow of inert gas and held at 180° C. for at least 1 h, thencooled to room temperature. The amount of adsorbed pyridine on Brønstedand Lewis acid sites, was determined using the difference in theinfrared spectra after the outgassing at 450° C. and desorbing thepyridine at 180° C., by making use of the correspondingpyrimidinium-band and pyridine Lewis acid band with known extinctioncoefficients.

Dispersion

The dispersion degree can be determined by measuring the amount of COadsorbed on a sample in reduced form of the catalyst at 25° C. and apressure of 1 bar as follows. A known amount of a sample of the catalystis placed in a reactor and reduced with hydrogen at 200° C. Aftercooling in hydrogen to 25° C., the reactor is flushed with helium for atleast 30 minutes. Subsequently, the helium stream is interchanged withsix pulses of a known amount of CO and the concentration of CO ismeasured at the outlet of the reactor with a thermal conductivitydetector. The amounts of catalyst and CO are chosen such that thecatalyst is saturated with CO after the first pulse, the second throughsixth pulse are used to verify this.

The upper limit for the dispersion degree corresponds to the theoreticalnumber of CO atoms that can be bound to one noble metal (Pt, Ir, Ru, Rhor Pd) atom. For practical purposes a value of 1 is generally a suitableupper limit.

The invention is further elucidated on the basis of the following, nonrestrictive, example.

Catalyst Preparation

A support containing 30% zeolite Y by weight was prepared from zeoliteHY powder and solutions of silica and aluminum-sulfate by an aqueoussol-gel technique. The thus obtained spheres are designated MVS052.Brønsted acidity of MVS052 was 312 μmol/g as determined by pyridineadsorption at RT and desorption at 18° C. MVS052 was impregnated with anaqueous solution containing Pd and Pt. After drying and reduction acatalyst designated MVC069 was obtained. The Pd content was 0.89% byweight. The Pt content was 0.30% by weight. The dispersion degree was0.23.

Hydrocarbon Conversion

MVC069 was loaded in a fixed bed reactor and contacted with ahydrocarbon stream at 50 bar total pressure, a reactor inlet temperatureof 260° C., a LHSV of 1.5 l/h and a hydrogen GHSV of 750 l/h. Theproperties of the feed and the product are listed in the table.

Feed Product Sulphur [ppm] 65 21 Nitrogen [ppm] 120 15 Boiling range [°C.] [ASTM D 86]  5% 241 237 95% 356 361 Total Aromatics [%] IP 391/9530.0 17.8 Mono 20.6 16.6 Di 7.2 1.0 Tri 2.2 0.2 Density [g/ml] 0.85480.8445 15° C. Cetane IP380 52.4 56.3

1. A catalyst for the hydrogenation, hydro-isomerisation, hydrocrackingand/or hydrodesulfurisation of hydrocarbon feedstocks comprising: asubstantially binder free support material comprising homogenous beadshaving 5 to 60 wt. % of at least one crystalline molecular sievematerial and 40 to 95 wt. % of non-crystalline, non-zeoliticsilica-alumina, the support having a Bronsted acidity of at least 50μmol/g, a surface area from 25 to 1200 m²/g, and an average pore size ofhigher than 2 nm, and the silica-alumina having an X-ray diffractionpattern which does not exhibit any diffraction peaks with a width athalf height less than 1.0 degree of arc when measured over the doublediffraction angle; and a catalytically active component comprisingprecious metals, wherein the catalyst has a dispersion degree of atleast 0.2.
 2. The catalyst of claim 1, wherein the support materialconsists of 10 to 50 wt. % of at least one molecular sieve material and50 to 90 wt. % of non-crystalline, non-zeolitic silica-alumina.
 3. Thecatalyst of claim 1, wherein the non-crystalline, non-zeoliticsilica-alumina in the support material is an acidic silica-aluminaobtained by sol-gel techniques and the ratio of Si to Al is from 1:10 to200:1.
 4. The catalyst of claim 1, wherein the molecular sieve materialcomprises one or more of zeolites and modified zeolites.
 5. The catalystof claim 1, wherein the catalyst contains 0.01 to 5 wt. % of preciousmetal, calculated in the weight of the catalyst as catalytically activecomponent.
 6. The catalyst of claim 1, wherein the catalytically activecomponent comprises at least one component selected from the group ofplatinum, palladium, ruthenium, iridium and rhodium.
 7. The catalyst ofclaim 6, wherein the catalytically active component is selected from thegroup comprising platinum, palladium or combinations thereof.
 8. Thecatalyst of claim 7, wherein the catalytically active componentcomprises platinum and palladium in a weight ratio of 10:1 to 1:10.
 9. Acatalyst for the hydrogenation, hydro-isomerisation, hydrocrackingand/or hydrodesulfurisation of hydrocarbon feedstocks, the catalystcomprising: a substantially binder free bead type support materialcomprising 5 to 60 wt. % of at least one crystalline molecular sievematerial and 40 to 95 wt. % of non-crystalline, non-zeoliticsilica-alumina, the substantially binder free bead type support materialobtained through dropwise addition of an aqueous sol of inorganic saltsof aluminum and silicon, having dispersed therein the crystallinemolecular sieve material, through an oil-phase to a water phase,providing homogeneous beads that are obtained without a separateshape-forming step; and a catalytically active component comprisingprecious metals.
 10. The catalyst of claim 9, wherein the supportmaterial consists of 10 to 40 wt. % of at least one molecular sievematerial and 60 to 90 wt. % of non-crystalline, non-zeoliticsilica-alumina.
 11. The catalyst of claim 9, wherein thenon-crystalline, non-zeolitic silica-alumina in the support material isan acidic silica-alumina, and the ratio of Si to Al is from 1:10 to200:1.
 12. The catalyst of claim 9, wherein the molecular sieve materialcomprises one or more of zeolites and clay minerals.
 13. The catalyst ofclaim 9, the support having a Bronsted acidity of at least 50 μmol/g, asurface area from 25 to 1200 m²/g, and an average pore size of higherthan 2 nm, and the silica-alumina having an X-ray diffraction patternwhich does not exhibit any diffraction peaks with a width at half heightless than 1.0 degree of arc when measured over the double diffractionangle.
 14. The catalyst of claim 9, wherein the catalyst contains 0.01to 5 wt. % of precious metal, calculated in the weight of the catalystas catalytically active component.
 15. The catalyst of claim 9, whereinthe catalytically active component comprises at least one componentselected from the group of platinum, palladium, ruthenium, iridium andrhodium.
 16. The catalyst of claim 15, wherein the catalytically activecomponent is selected from the group comprising platinum, palladium orcombinations thereof.
 17. A method of making a catalyst supportcomprising: providing an aqueous sol comprising inorganic salts ofaluminum and silicon, wherein at least one crystalline molecular seizematerial is dispersed in the aqueous sol; adding droplets of the aqueoussol to an oil phase to provide a substantially binder free bead shapedcatalyst support comprising the molecular sieve material andnon-crystalline, non-zeolitic silica-alumina, the beads obtained withouta separate shape-forming step.
 18. The method of claim 17, wherein thesubstantially binder free bead shaped catalyst support comprises 5 to 60wt. % of the crystalline molecular sieve material and 40 to 95 wt. % ofthe non-crystalline, non-zeolitic silica-alumina.
 19. The method ofclaim 17, further comprising passing the sol droplets through a waterphase after adding them to the oil phase.
 20. The method of claim 17,further comprising applying a catalytically active component comprisingprecious metals to the catalyst support.